Method for forming a vertical electrical connection in a layered semiconductor structure

ABSTRACT

The invention proposes a method for forming a vertical electrical connection ( 50 ) in a layered semiconductor structure ( 1 ), comprising the following steps: —providing ( 100 ) a layered semiconductor structure ( 1 ), said layered semiconductor structure ( 1 ) comprising: —a support substrate ( 20 ) including an first surface ( 22 ) and a second surface ( 24 ), —an insulating layer ( 30 ) overlying the first surface ( 22 ) of the support substrate ( 20 ), and —at least one device structure ( 40 ) formed in the insulating layer ( 30 ); and —drilling ( 300 ) a via ( 50 ) from the second surface of the support substrate ( 20 ) up to the device structure ( 40 ), in order to expose the device structure ( 40 ); characterized in that drilling ( 300 ) of the insulating layer is at least performed by wet etching ( 320 ).

FIELD OF THE INVENTION

The present invention generally relates to a method for making atransverse electrical connection in a layered semiconductor structure.

More particularly, the invention concerns the manufacture of vias in anintegrated circuit.

BACKGROUND OF THE INVENTION

The main application of the invention resides in the field ofmicroelectronics, for the metallization, particularly with copper, ofvias (called “through-silicon vias” (TSV) or “through-wafer vias” or“through-wafer interconnects”), the keystone for the three-dimensional(3D) integration, or vertical integration, of electronic chips (ordies). Such vias have typical hole size ranging between 0.5 μm and 500μm, most commonly between 5 μm and 100 μm; and typical depth rangingbetween 10 μm and 750 m, most commonly between 50 μm and 300 μm. It alsohas applications in other fields of electronics where a substratecomprising vias must be electrically insulated and covered with a layerof copper. In this context can be mentioned the formation ofinterconnecting elements between printed circuit boards (or printed wireboards), of passive elements such as inductors, or of electromagneticelements in integrated circuits or micro-electromechanical systems, orof metallization schemes for photovoltaic cells

Current electronic systems mostly consist of several integratedcircuits, or components, and each integrated circuit fulfils one or morefunctions. For example, a computer comprises at least one microprocessorand several memory circuits. Each integrated circuit usually correspondsto an electronic chip in its own package. The integrated circuits aresoldered to or plugged into, for example, a printed circuit board (PCB)which ensures the connection between the integrated circuits.

The permanent need to increase the functional density of electronicsystems has led, according to a first approach, to the so-called“system-on-chip” concept, with all the components and circuit unitsnecessary to implement all the system functions being produced on thesame chip without using a printed circuit support. In practice it isnonetheless very difficult to obtain a high-performance system-on-chipas the manufacturing methods for logic and memory circuits, for example,differ very substantially from each other. The system-on-chip approachtherefore requires the acceptance of compromises with respect to theperformance of various functions produced on the same chip. In addition,the size of such chips and their manufacturing efficiency are reachingthe limits of their economic feasibility.

A second approach consists in forming in one and same package a moduleensuring the interconnection of several integrated circuits, which maybe formed on the same semiconductor substrate or on differentsubstrates. The package thus obtained, or the multichip module (MOM) orSystem-in-Package (SiP) or System-On-a-Package (SOP), thus takes theform of a single component. This MOM approach makes it possible toobtain a higher interconnection density and therefore better performancethan a conventional PCB approach. It is however not fundamentallydistinguished from the PCB approach. Apart from the bulk and the weightof the package, the performance of an MOM remains limited by theelectromagnetic interferences associated with the length of theconnections from the substrate and with the wire bonds connecting thesubstrate or the chips to the pins of the package.

A third approach, called three-dimensional (3D) integration or verticalintegration, is characterized by the fact that the chips are stacked andconnected to each other by vertical interconnections drilled through thechip's material, electrically connecting the top surface with the bottomsurface of the chip. The stack obtained thus comprises several layers orstrata of active components or chips, and constitutes a 3D integratedcircuit (or 3D IC).

The benefits of 3D integration are based on:

(1) improvement in performance, e.g. reduction in propagation time andin dissipated power, increase in the operating speed of the systemassociated with the accelerated communication between the functionalunits, increase in the bandwidth of each functional unit, increase innoise immunity;

(2) improved cost-effectiveness, e.g. increase in integration density,improved manufacturing efficiency due to the use of the electronic chiptechnology which is most appropriate for each functional unit, improvedreliability; and

(3) the possibility of producing highly integrated systems by stackingheterogeneous technologies (or co-integration), i.e. employing differentmaterials and/or different functional components.

As a result, 3D integration today constitutes an essential alternativeto the conventional approaches, which are reaching their limits in termsof performance, functional diversification and production costs. Thefoundations and advantages of 3D integration have been described, forexample, in: A. W. Topol et al., “Three-dimensional integrated circuits”IBM Journal Res. & Dev., no. 4/5 July/September 2006, 50, 491-506.

After stacking, for example by bonding, the chips may be individuallyconnected to the pins of the package by wire bonding or flip-chipconnections. The interconnections between the chips are generallycarried out by employing TSVs.

The elementary technologies necessary for the production of 3Dintegrated circuits comprise in particular thinning the silicon wafers,aligning the layers, bonding the layers, and etching and metallizing theTSVs within each layer.

The thinning of silicon wafers may be carried out before forming theTSVs (e.g. U.S. Pat. No. 7,060,624, U.S. Pat. No. 7,148,565).

Alternatively, the etching and the metallization of vias may be carriedout before thinning the silicon wafer (e.g. U.S. Pat. No. 7,060,624,U.S. Pat. No. 7,101,792). In this case, closed vias or blind vias areetched in the silicon on one side of the wafer to the desired depth,then metallised throughout before thinning the silicon wafer from theother side in order to expose the buried end of the metallization andthus obtain through-silicon vias.

The good electrical conductivity of copper and its high resistance toelectro-migration, i.e. the low tendency of copper atoms to migrateunder the effect of the electrical current density, which can be animportant cause of failure, make it in particular a material of choicefor the metallization of vias.

The vias of 3D integrated circuits are generally made in a mannersimilar to the “Damascene method” used in the field of microelectronicsfor forming elements for interconnecting integrated circuits, accordingto a series of steps comprising:

the etching of vias in or through the silicon wafer and through theBack-End-Of-Line (BEOL) stack if necessary (e.g. for via-laststructures);

the deposition of an insulating dielectric layer, or liner;

the deposition of a barrier layer, serving to prevent the migration ordiffusion of copper;

the optional deposition of a seed layer to improve theelectro-deposition of copper in case the selected barrier material has avery low electrical conductivity

the filling of the vias by electro-deposition of copper; and

the elimination of excess copper and barrier from the wafer surface bychemical-mechanical polishing.

As mentioned above, the invention is more particularly directed to thefabrication of “via-last structures”, i.e. TSVs formed in the integratedcircuit, following the BEOL steps, by opposition with “via first” (whichare formed prior to the front-end-of-line (FEOL) steps) and “via middle”(which are formed following FEOL steps but prior to the BEOL steps).

The “via first” method involves forming the TSVs in a substrate beforeany other fabrication of circuitry occurs. A pattern of vias is etchedor drilled into a fraction of the depth of the base substrate. The viasare then filled with an insulating layer and conducting material andcircuit manufacturing follows. One or more dies can then bond to theTSVs. The back side of the substrate containing the TSVs is ground downto expose the TSVs. Metallization of the exposed TSVs enables packagingof the multi-tiered structure.

In the “via last” method, circuit manufacturing and optional waferthinning take place before the TSVs are formed. The circuitry containsinterconnect conductive pads that will be coupling points for the TSVs.TSVs are created by either etching or drilling to the conductive padthrough the depth of the substrate or etching or drilling from the backside of the substrate to the conductive pad. The TSV is then filled withan insulating layer and conducting material. The back of the substrateis metalized to enable packaging of the multi-tiered structure.

The distinction between the different kinds of TSVs being well-known bythe skilled person, it will not be further discussed here. Nevertheless,one can refer to “Handbook of 3D Integration: Technology andApplications of 3D Integrated Circuits”, Ph. Garrou et al., WILEY-VCH,2009 in order to have additional information.

Usually, via-last TSVs are formed in accordance with the followingsteps:

providing a layered semiconductor structure, said layered semiconductorstructure comprising:

a support substrate including a first surface and a back surface,

at least one insulating layer overlying the first surface of the supportsubstrate; most commonly a stack of insulating layers from differentmaterials is used; and

at least one conductive pad formed within the insulating layer; and

drilling a via from the back surface of the support substrate.

The drilling is usually formed by dry etching, in order to obtainstraight walls for the via and thus facilitate the uniform coating ofthe via with the insulating layer.

However, different materials must be etched (typically a firstinsulation layer, the wafer silicon bulk, and the layered semiconductorstructure described above), so different methods and tools must be usedin a predetermined sequence. The limitation of this method is linked tothe difficulty of stopping the process at the right moment, i.e. tocompletely remove the required material without damaging the metal padand to avoid the resputtering of its conductive material (usually,copper), i.e. ejection of conductive material towards the walls of thevia, which can later induce short-circuits at the active device'sjunctions due to the diffusion of unwanted copper ions into the siliconbulk.

As a consequence, in spite of the aforementioned drawbacks, dry etchingis still privileged over other known techniques since it is a simple andcommon way to rapidly obtain a straight via in an integrated circuit.

An insulating film is then coated on the via walls by conventionaltechniques such as deposition. These methods however also coat theconductive pad and the existing insulating layer(s), so that anadditional step to remove the insulating film at least from theconductive pad becomes necessary, in order to enable connection with thecomponents.

There is therefore a need for a method that overcomes the aforementioneddrawbacks.

SUMMARY OF THE INVENTION

An objective of the invention is to provide a method for preciselyforming a good through electrical connection in a layered semiconductorstructure that avoids resputtering and guarantees the exposition of thedevice structure in a few steps.

To this end, the invention proposes a method for forming a verticalelectrical connection in a layered semiconductor structure, comprisingthe following steps:

providing a layered semiconductor structure, said layered semiconductorstructure comprising:

a support substrate including a first surface and a second surface (24),

an insulating layer overlying the first surface of the supportsubstrate, and

at least one device structure formed in the insulating layer; and

drilling a via from the second surface of the support substrate (20) upto the device structure, in order to expose the device structure;

characterized in that drilling of the insulating layer is at leastpartially performed by wet etching.

Some preferred but non limiting aspects of the invention are thefollowing:

wet etching is performed during a predetermined time, said predeterminedtime depending on the material of the insulating layer, the etchant andthe thickness of the insulating layer to be drilled;

wet etching is performed with a solution containing fluorhydric acid,and optionally glycerol;

the etchant comprises between 0.5% and 50% in volume of fluorhydricacid, preferably 1.35%;

the etchant further comprises between 0.5 and 50% in volume of glycerol,preferably 1.35%;

the method further comprises a pre-wetting step prior to the wet etchingstep (320), wherein the layered semiconductor structure is plunged inwater;

a rinsing step following the wet etching step, wherein the layeredsemiconductor structure is rinsed with water;

the method further comprises a vacuum step following the wet etchingstep, wherein the layered semiconductor structure is submitted to acontrolled vacuum;

the layered semiconductor structure is plunged in water during thevacuum step;

the method further comprises a removal step before the wet etching step,wherein the support substrate is thinned;

the method further comprises a pre-drilling step before the wet etchingstep, wherein a pre-via is formed from the second surface up to at leastthe insulating layer; and

the pre-via is formed by dry etching, wet etching or reactive ionetching.

In accordance with a second aspect, the invention proposes a method forfabricating a vertical connection in a layered semiconductor structure,comprising the following steps:

forming the vertical connection in the layered semiconductor structurein accordance with the above-mentioned method, and

wet coating the vertical connection with an insulating film by bringinga surface of said vertical connection into contact with a liquidsolution.

Preferred but non limiting aspects of the method of the invention arethe following:

the wet coating solution comprises:

a protic solvent;

at least one diazonium salt;

at least one monomer that is chain-polymerizable and soluble in saidprotic solvent;

at least one acid in a sufficient quantity to stabilize said diazoniumsalt by adjusting the pH of said solution to a value less than 7,preferably less than 2.5; and

the surface of said vertical connection is polarizes according to apotentio- or galvano-pulsed mode for a duration sufficient to form afilm having a thickness of at least 60 nanometers, and preferablybetween 80 and 500 nanometers;

the method further comprises the preparation of a copper diffusionbarrier by:

a) forming by a wet process, at the surface of the insulating film, anorganic film containing particles, especially nanoparticles, of metalsor metal alloys, in particular of nickel or cobalt;

b) bringing the film thus formed into contact with a liquid solutioncontaining at least one metal salt, preferably of the same nature as themetal incorporated into the organic film, a stabilizing agent, and atleast one reducing agent under conditions enabling the formation of ametal film having a thickness of at least 100 nm;

the method further comprises the preparation (500) of a copper diffusionbarrier by:

-   1. activating the surface of the insulating layer with a solution    comprising:    -   i) an activator constituted of one or several palladium        complexes chosen in the group consisting of:    -   palladium complexes having the formula (I):

-   -   wherein:        -   R1 and R2 are identical and represent H; CH₂CH₂NH₂;            CH₂CH₂OH; or        -   R1 represents H and R2 represents CH₂CH₂NH₂; or        -   R2 represents CH2CH2NHCH2CH2NH2 and R1 represents CH₂CH₂NH₂;            or        -   R2 represents CH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂ and R1 represents H;        -   X represents a ligand chosen in the group consisting of Cl⁻;            Br⁻; I⁻; H₂O, NO₃ ⁻; CH₃SO₃ ⁻; CF₃SO₃ ⁻; CH₃-Ph-SO₃ ⁻;            CH₃COO⁻;    -   palladium complexes having the formula (IIa) or (IIb):

-   -   wherein:        -   R1 and R2 are defined as above-mentioned, and        -   Y represents a counter-ion comprising two negative charges            constituted:    -   either of two mono-anions preferably chosen in the group        consisting of Cl⁻; PF₆ ⁻; BF₄ ⁻; NO₃ ⁻; CH₃SO₃ ⁻; CF₃SO₃ ⁻;        CH₃C₆H₄SO₃ ⁻; CH₃COO⁻; or    -   of a di-anion, preferably SO₄ ²⁻;    -   ii) an bi-functional organic binder constituted of one or        several organosilanes having the general formula:        {NH₂-(L)}_(3-n)-Si(OR)_(n)  (V)    -   wherein:        -   L is a spacer selected from the group consisting of CH₂;            CH₂CH₂; CH₂CH₂CH₂— and CH₂CH₂NHCH₂CH₂;        -   R is a group selected from the group consisting of CH₃,            CH₃CH₂, CH₃CH₂CH₂, (CH₃)₂CH; and        -   n is an integer equal to 1, 2 or 3.    -   iii) a solvent system constituted of one or several solvents        suitable for solubilising said activator and said binder;

-   2. electrolessly depositing a metallic layer on the activated    surface.    -   the method further comprises further comprising the preparation        of a copper seed layer by:    -   a) bringing the free surface of the copper diffusion barrier        layer into contact with a liquid solution comprising:    -   at least one solvent;    -   copper ions in a concentration of between approximately 14 and        120 mM;    -   ethylenediamine;    -   the molar ratio of ethylenediamine to copper being between 1.80        and 2.03;    -   the pH of said composition being between 6.6 and 7.5;    -   b) polarizing said free surface of the second layer for a        sufficient duration to form said copper seed layer;    -   the method further comprises a step of metallization of the        vertical electrical connection by electrodepositing copper with        a composition comprising:    -   copper ions, said copper ions having a concentration of 45 to        1500 mM, preferably 45 to 500 mM, and more preferably 100 to 300        mM;    -   a complexing agent for copper, comprising at least one component        of the group comprising the aliphatic polyamines having 2 to 4        amino groups, said complexing agent for copper having a        concentration of 45 to 3000 mM, preferably 45 to 1500 mM, and        more preferably 300 to 900 mM; The complexing agent for copper        can be, for example, ethylenediamine, diethylenediamine,        triethylenediamine or dipropylenetriamine, preferably        ethylenediamine.    -   the molar ratio between copper and said complexing agent for        copper being of 0.1 to 5, preferably 0.1 to 1, and more        preferably 0.2 to 0.4;    -   thiodiglycolic acid, said thiodiglycolic acid having a        concentration of 1 to 500 mg/L; and    -   optionally, a buffering system, in particular ammonium sulphate,        in a concentration of 0.1 to 3 M.

In accordance with a third aspect, the invention proposes a layeredsemiconductor structure comprising:

a support substrate including an first surface and a second surface,

an insulating layer overlying the first surface of the supportsubstrate,

at least one device structure formed in the insulating layer; and

at least one vertical connection, extending from the second surface ofthe support substrate up to the device structure,

characterized in that the vertical connection comprises an undercut inthe vicinity of the first surface of the support substrate obtainable inaccordance with the aforementioned method.

Preferred but non-limiting aspects of the invention are the following:

the method further comprises at least an insulating film applied on thewalls of the vertical connection in the vicinity of the supportsubstrate (30), wherein said insulating layer has a uniform thicknessand is obtained in particular by the aforementioned method;

the method further comprises a copper diffusion barrier over theinsulating layer and the walls of the vertical connection, wherein saidcopper diffusion barrier has a uniform thickness and is obtained inparticular by the aforementioned method;

the method further comprises a copper seed layer (80) over the copperdiffusion barrier (70), wherein said copper seed layer (80) has auniform thickness and is obtained in particular by the aforementionedmethod;

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention will now be described, by way of example,with reference to the accompanying drawings in which:

FIGS. 1 to 6 represent a sectional view of an example of semiconductorstructure during the different steps of a method in accordance with theinvention;

FIG. 3A is a close-up of one of the undercuts of FIG. 3; and

FIG. 7 is a flowchart of the steps of a method for forming a verticalelectrical connection in the semiconductor structure of FIGS. 1 to 6 inaccordance with an embodiment of the invention.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

As used herein, the term “semiconductor structure” means any structurethat is used in the formation of a semiconductor device. Semiconductorstructures include, for example, dies and wafers (for example, carriersubstrates and device substrates), as well as assemblies or compositestructures that include two or more dies and/or wafersthree-dimensionally integrated with one another. Semiconductorstructures also include fully manufactured semiconductor devices, aswell as intermediate structures formed during manufacture ofsemiconductor devices. A method for forming a vertical electricalconnection in a layered semiconductor structure in accordance with theinvention is illustrated in FIG. 1.

As used herein, the term “device structure” means and includes anyportion of a processed semiconductor structure that constitutes,includes, or defines at least a portion of an active or passivecomponent of a semiconductor device to be formed on or in thesemiconductor structure. For example, device structures include activeand passive components of integrated circuits such as, for example,transistors, transducers, capacitors, resistors, conductive lines,conductive vias, and conductive contact pads.

As used herein, the term “active surface,” when used in relation to aprocessed semiconductor structure, means and includes an exposed majorsurface of the processed semiconductor structure that has been, or willbe, processed to form one or more device structures in and/or on theexposed major surface of the processed semiconductor structure.

As used herein, the term “back surface,” when used in relation to aprocessed semiconductor structure, means and includes an exposed majorsurface of the processed semiconductor structure on an opposing side ofthe processed semiconductor structure from an active surface of thesemiconductor structure.

In one embodiment, as shown in FIG. 1, the present invention includesproviding a semiconductor structure 1 having an active surface 2 and aback surface 4. The active surface 2 may be on a first side of the firstsemiconductor structure 1, with the back surface 4 on a second, oppositeside.

The semiconductor structure 1 comprises:

a support substrate 20 including a first surface 22 and a second surface24,

an insulating layer 30 overlying the first surface of the supportsubstrate, and

at least one device structure 40 formed in the insulating layer.

The support substrate 20 may comprise, for example, one or moresemiconductor materials such as Silicon (Si), Gallium (Ga), etc. and hasa thickness of about 10 μm to about 750 μm. Here, the second surface 24of the support substrate 20 corresponds to the back surface 4 of thesemiconductor structure 1.

The insulating layer 30 has a thickness generally of about 1 μm to 20μm, and can be made of Silicon Oxide (SiO₂), Silicon Oxycarbide (SiOC),hydrogenated Silicon Oxycarbide (SiOCH), Silicon Carbide (SiC), SiliconNitride (SiN) or a mixture thereof.

Finally, the device structure 40 is here a conductive pad.

The conductive pad 40 is made of a conductive material such as Copper(Cu), Aluminum (Al), or an alloy comprising Aluminum and Copper.

The conductive pad 40 can further be coated with a barrier layer 45 ofabout 5 nm to 200 nm, in order to prevent diffusion of the conductivematerial. The barrier layer 45 can be made of titanium nitride (TiN),tantalum nitride (TaN), titanium or tantalum.

In the following, we will describe an embodiment of a method for forminga vertical electrical connection 50 in the semiconductor structure 1.

In a first step 100, a layered semiconductor structure 1 is provided.

Optionally, in a second step 200, the semiconductor structure 1 may bethinned by removing material from the second surface 24 of the supportsubstrate 20. For example, the semiconductor structure 1 may be thinnedusing a chemical process (e.g., a wet or dry chemical etching process),a mechanical process (e.g., a grinding or lapping process), or by achemical-mechanical polishing (CMP) process.

As a non-limiting example, the support substrate 20 can be thinned inorder to reduce its thickness to about 50 μm.

Preferably, the active surface 2 of the semiconductor structure 1 isthen bonded to a carrier 35 adapted to bring mechanical strength to thestructure 1. Such a carrier 35 can be made of silicon oxide or silicon.An example of semiconductor structure 1 comprising such a carrier isshown in FIG. 1.

In a third step 300 (see FIGS. 2 to 3), the vias 50 are then formed inthe semiconductor structure 1.

Formation of the vias 50 is performed by drilling a via from the secondsurface 24 of the support substrate 20 up to the conductive pad 40, inorder to expose the conductive pad 40.

In accordance with the invention, drilling is performed by drillingfirst 310 the support substrate 20, in order to obtain a pre-via 52which extends from the second surface 24 of the support substrate 20 toan area adjacent to the interface of the support substrate 20 with theinsulating layer 30 (FIG. 2), and then by wet etching 320 the insulatinglayer 30 (FIG. 3).

Advantageously, forming a pre-via 52 in the support substrate 20simplifies the wet etching step 320 if the etchant is chosen to beselective and does not react with the material of the support substrate20. The use of a mask, which is conventional in wet etching whenever aspecific shape is needed, is therefore pointless since in any case theetchant will only etch the insulating layer 30.

Drilling 300 of the pre-via 52 can be performed by any known techniquesuch as dry etching, wet etching with an appropriate etchant, orreactive ion etching.

In accordance with a first embodiment, the pre-via extends from the backsurface 4 to the first surface 22 of the support substrate.

Alternatively, the pre-via extends into the layer 30 up to an areaadjacent to, but not in contact with, the barrier layer 45. In thatcase, the wet etching step 320 only drills the remaining thickness ofinsulating layer 30 in order to expose the barrier layer 45 of theconductive pad 40.

The etchant used during the wet etching step 320 of the insulating layer30 can be fluorhydric acid, ammonium fluoride, a mixture thereof such asBuffered Oxide Etch (BOE) or any etchant adapted to selectively etch thematerial of the insulating layer 30 and not the material of the barrierlayer 45 or the conductive material 40. For example, the etchantcomprises between 0.1% and 50% by volume of fluorhydric acid, preferablybetween 0.1 and 2.5%, and the balance of deionized or distilled water.In this solution, polyols compounds suchs as glycerol, cathecol,ethyleneglycol or polyethyleneglycol, polypropylenalcohol, polyvinylalcohol can be added to enhance the etch selectivity between thematerial of the insulating layer 30 and the material of the barrierlayer 45. For example, the etchant comprises between 0.1 and 2.5% byvolume of fluorhydric acid and between 0.1 and 2.5% by volume ofglycerol and the balance of deionized or distilled water.

The wet etching step 320 is performed during a predetermined time whichdepends on the etchant, the material and the thickness of insulatingmaterial to be drilled.

For example, for an etchant comprising 1.75% of fluorhydric acid and aninsulating layer made of SiO₂ CVD, the etching rate is about 120 nm/min.

More generally, the higher the concentration of fluorhydric acid in theetchant, the faster the etching rate.

The duration of the wet etching step 320 can therefore be preciselydetermined based on the thickness of SiO₂ to be etched so that via 50 besufficiently deep in order to expose the barrier layer 45 of theconductive pad 40 without damaging said pad 40.

In addition, the choice of an etchant adapted to selectively etch thematerial of the insulating layer 30 and not the material of the barrierlayer 45 of the conductive pad 40 further improves the accuracy of theprocess. In the aforementioned example, fluorhydric acid with addedglycerol is selective since its etching rate of the barrier layermaterial is extremely slow by contrast with the etching rate of SiO₂. Asa consequence, knowing the etching rate and the thickness of SiO₂ to beetched allows the exposition of the barrier layer 45 of the conductivepad 40 without damaging them, and without provoking resputtering oftheir constitutive materials. This effect can be strongly enhanced byusing polyol compounds such as glycerol in the etchant. The polyolcompounds will protect the barrier layer 45 from the fluorhydric acid.The selectivity can be thus increased by a factor of 200 based on theconventional etching rate.

Etchants such as fluorhydric acid being hydrophobic with Silicon, themethod can further comprise a pre-wetting step 322, in order to improvethe wet etching step 320. In that purpose, the semiconductor structure 1is plunged into deionized or distilled water prior to the drilling ofthe vias 50 in the insulating layer 30, so that the etchant betterdiffuses inside the pre-vias 52.

Besides, at the end of the wet etching step 320, the semiconductorsubstrate can be rinsed (324) in deionized or distilled water, immersed(326) in fresh deionized or distilled water and then submitted 328 tovacuum, in order to stop the etching reaction and guarantee that theconductive pad 40 is not damaged and its material does not redeposittowards the walls of the via 50.

The vacuum step 328 can last for example from 1 to 10 minutes, under avacuum of about 1 to 100 mbar.

EXAMPLE

Coupons (2*2 cm) of vias of 75×45 μm were first submitted to thepre-wetting step 322. They were then immediately immersed in an etchantcomprising 1.35% by volume of fluorhydric acid (0.72 M) and 1.35% byvolume of glycerol. Dilution of the etchant is chosen to have a goodcontrol in time of the etching. Indeed, when concentration of theetchant is too high, the barrier layer can also be attacked if thecoupon is not extracted from the etchant at the right moment. Here, witha concentration of 1.35% by volume of fluorhydric acid, selectivity ofthe etchant remains good and limits the risk of etching the barrierlayer.

Alternatively, glycerol can be further added to the fluorhydric acid inorder to increase the etch selectivity between the oxide and the barrierlayer. Indeed, an etchant comprising fluorhydric acid and glycerol willnot etch the barrier layer, even if the coupon is left longer in theetchant (i.e during a period of time longer that the time necessary todrill the insulating layer 30 up to the pad).

At the desired time, the coupon is then rapidly rinsed (324) withdeionized water, immersed (326) in fresh deionized water and subjected(328) to vacuum.

The resulting etch rate for the SiO₂ encountered in the bottom of thevias is about 40 nm/min.

For 800 nm of SiO₂ over the pad, we tested etching times of 16 min. and18 min. The first etching time led the etching to around 80 nm over thepad and the second led the etching to exactly the top of the pad leadingto the exposure of the latter.

At the end of the drilling step 300, the semiconductor substrate 1comprises vias 50 extending from the active surface 2 to the barrierlayer 45 (or the conductive pad 40, if the semiconductor substrate 1does not comprise such a barrier layer 45).

Etching is however isotropic, so that the material of the insulatinglayer 30 is etched at a similar etching rate in every direction, therebyforming an undercut U in the area adjacent to the beginning of the wetetching step 320 (i.e. at the interface between the support substrate 20and the insulating layer 30 when the pre-via extends up to the firstsurface 22 of the support substrate 20). An example of such an undercutis visible in FIGS. 3 and 3A.

For the above-mentioned via 50, the ratio between the transversedimension a and the longitudinal dimension b of the undercut U is lyingbetween 1 to 1.1.

Coating the walls of the via 50 in accordance with the conventionaldeposition methods is therefore difficult since they are not straight.

This is the reason why wet etching has never been considered as anoption for drilling vias last. The unavoidable occurrence of theundercut U actually taught away the skilled person from realizing viasby wet etching.

The occurrence of the undercut U can however be compensated byperforming a wet coating of the walls of the via 50.

Wet coating is a selective method which allows selectively coating thewalls of the via 50 in the area of the support substrate 30.

Advantageously, this method allows the coating of an insulating layer 60(FIG. 4), a copper diffusion barrier 70 (FIG. 5) and a copper seed layer80 (FIG. 6) of uniform thicknesses, whatever the shape of the wallswherein the coating has to be applied. In addition, by adequatelychoosing the solution used during the coating of the insulating film 60,the method can be selective and only coat the walls of the vias in thevicinity of the support substrate 30. By contrast, the layers 70 and 80obtained by wet coating successively cover, with a uniform thickness,the whole surface of the via (50), i.e. the walls in the vicinity of thesupport layer 30 (already covered with the insulating film 60), thewalls in the vicinity of the insulating layer 30, and the bottom of thevia 50 (in the vicinity of the conductive pad 40).

Finally, this method is very efficient and allows the coating of severalvias 50 at the same time.

An example of a wet coating method is known from document WO 2010/001054in the name of the Applicant.

The method described in this document allows selective coating of thevia 50 with an insulating film 60 (step 400—FIG. 4).

The semiconductor substrate 1 which is obtained in accordance with thismethod thus comprises vias 50 uniformly coated with the insulating film60 in the vicinity of the support substrate 20 only and not on theinsulating layer 30 nor on the conductive pad 40 (or its barrier layer45), without necessitating any additional steps of removal of theinsulating film deposited on the conductive pad 40 or the insulatinglayer 30.

The method described in WO 2010/001054 also allows the preparation of acopper diffusion barrier 70 (step 500—FIG. 5), optionally of a copperseed layer 80 (step 600—FIG. 6) and its metallization by filling withcopper, in spite of the undercut U.

More precisely, WO 2010/001054 describes the preparation (step 400) ofan electrically insulating film 60 at the surface of an electricalconductor or semiconductor substrate, such as the support substrate 20,comprising:

a) bringing said surface into contact with a liquid solution comprising:

-   -   a protic solvent;    -   at least one diazonium salt;    -   at least one monomer that is chain-polymerizable and soluble in        said protic solvent;    -   at least one acid in a sufficient quantity to stabilize said        diazonium salt by adjusting the pH of said solution to a value        less than 7, preferably less than 2.5;

b) the polarization of said surface according to a potentio- orgalvano-pulsed mode for a duration sufficient to form a film having athickness of at least 80 nanometers, and preferably between 100 and 500nanometers.

The protic solvent used can be chosen from the group consisting ofwater, preferably deionized or distilled water, and hydroxylatedsolvents, in particular alcohols having 1 to 4 carbon atoms; carboxylicacids having 2 to 4 carbon atoms, in particular formic acid and aceticacid, and mixtures thereof.

Water constitutes the protic solvent currently preferred in the contextof the invention.

Generally speaking, many diazonium salts are capable of being used forthe implementation of the method according to this first aspect of theinvention, and in particular the diazonium salts mentioned in documentWO 2007/099218.

Thus, according to a particular characteristic, the diazonium salt is anaryldiazonium salt chosen from the compounds of the following formula(I):R—N₂ ⁺,A⁻  (I)

in which:

A represents a monovalent anion,

R represents an aryl group.

As an example of an aryl group R, it is possible in particular tomention the unsubstituted, mono- or polysubstituted aromatic orheteroaromatic carbon structures, consisting of one or more aromatic orheteroaromatic rings, each comprising 3 to 8 atoms, the heteroatom(s)being chosen from N, O, S, or P; the optional substituent(s) preferablybeing chosen from electron-attracting groups such as NO₂, CHO, ketones,CN, CO₂H, NH₂, esters and the halogens.

The use of an electrografting protocol in pulsed mode constitutesanother aspect of the method, to the extent that this particularprotocol makes it possible, completely unexpectedly and in contrast to acyclic voltammetry electrografting protocol, to obtain a continuous anduniform film with a growth kinetics compatible with industrialconstraints.

The method of preparing an electrically insulating film 60 which hasjust been described is especially useful in the preparation ofthrough-silicon vias 50, in particular of 3D integrated circuits, forconstituting the internal electrically insulating layer designed to becoated with the barrier layer 70 serving to prevent copper migration ordiffusion (step 500).

Advantageously, the aforementioned barrier layer 70 is itself producedby a wet deposition method, preferably in a liquid medium of proticnature for reasons that will straightforwardly be understood.

For such purpose, WO 2010/001054 discloses (step 500) a method ofpreparing a coating of the semiconductor substrate, said coatingconsisting of a first layer forming the electrically insulating film 60and a second layer forming the copper diffusion barrier 70, wherein thesecond layer is produced by:

a) the formation by wet process, at the surface of the first layer thusobtained, of an organic film containing particles, especiallynanoparticles, of metals or metal alloys, in particular of nickel orcobalt;

b) bringing the film 60 thus formed into contact with a liquid solutioncontaining at least one metal salt, preferably of the same nature as themetal incorporated into the organic film, and at least one reducingagent under conditions enabling the formation of a metal film having athickness of at least 20 nm.

Step a) is carried out by bringing the free surface of theaforementioned internal layer into contact with a liquid solutioncontaining:

at least one solvent, preferably a protic solvent;

at least one diazonium salt;

at least one monomer that is chain-polymerizable and soluble in saidsolvent; and

at least one chemical initiator enabling the formation of radicalentities from said diazonium salt.

The protic solvent and the diazonium salt employed in step a) may be ofthe same nature as the protic solvent used for the internal layer.

The use of an aprotic solvent, such as dimethylformamide, acetone ordimethyl sulphoxide, is nonetheless conceivable in the scope ofimplementing step. a).

The monomer that can be chain-polymerized by free radical methods mayvary in nature.

It will especially be chosen from the monomers described in WO2007/099218.

Alternatively, the barrier layer 70 can also be produced in accordancewith the following steps:

-   1. Activating the surface of the insulating layer with a solution    comprising:    -   i) an activator constituted of one or several palladium        complexes chosen in the group consisting of:    -   palladium complexes having the formula (I):

-   -   wherein:        -   R1 and R2 are identical and represent H; CH₂CH₂NH₂;            CH₂CH₂OH; or        -   R1 represents H and R2 represents CH₂CH₂NH₂; or        -   R2 represents CH2CH2NHCH2CH2NH2 and R1 represents CH₂CH₂NH₂;            or        -   R2 represents CH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂ and R1 represents H;        -   X represents a ligand chosen in the group consisting of Cl⁻;            Br⁻; I⁻; H₂O, NO₃ ⁻; CH₃SO₃ ⁻; CF₃SO₃ ⁻; CH₃-Ph-SO₃ ⁻;            CH₃COO⁻;    -   palladium complexes having the formula (IIa) or (IIb):

-   -   wherein:        -   R1 and R2 are defined as above-mentioned, and        -   Y represents a counter-ion comprising two negative charges            constituted:    -   either of two mono-anions preferably chosen in the group        consisting of Cl⁻; PF₆ ⁻; BF₄ ⁻; NO₃ ⁻; CH₃SO₃ ⁻; CF₃SO₃ ⁻;        CH₃C₆H₄SO₃ ⁻; CH₃COO⁻; or    -   of a di-anion, preferably SO₄ ²⁻;    -   ii) a bi-functional organic binder constituted of one or several        organosilanes having the general formula:    -   iii)        {NH₂-(L)}_(3-n)-Si(OR)_(n)  (V)    -   wherein:        -   L is a spacer selected from the group consisting of CH₂;            CH₂CH₂; CH₂CH₂CH₂— and CH₂CH₂NHCH₂CH₂;        -   R is a group selected from the group consisting of CH₃,            CH₃CH₂, CH₃CH₂CH₂, (CH₃)₂CH; and        -   n is an integer equal to 1, 2 or 3.    -   iv) a solvent system constituted of one or several solvents        suitable for solubilising said activator and said binder.

-   2. Electrolessly depositing a metallic layer on the activated    surface.

In accordance with an embodiment, the solution comprises water in anamount inferior or equal to 0.5%, preferably 0.2%, and more preferably0.1% in volume.

The activator has a concentration of 10⁻⁶ M and 10⁻² M, preferablybetween 10⁻⁵ M and 10⁻³ M, still more preferably between 5×10⁻⁵ M and5×10⁻⁴ M, and the binder has a concentration comprised between 10⁻⁵ Mand 10⁻¹ M, preferably between 10⁻⁴ M and 10⁻² M, still more preferablybetween 5×10⁻⁴ M and 5×10⁻³ M.

The bifunctional organic binder preferably consists of one or moreorganosilane compounds having the formula (V),

wherein:

L is CH₂CH₂CH₂— and R is CH₃ (APTMS);

or L is CH₂CH₂CH₂— and R is CH₃ (APTES);

or L is CH₂CH₂NHCH₂CH₂ and R is CH₃ (DATMS or DAMO).

The solvent system can consist of one or more solvents selected from thegroup consisting of N-methylpyrrolidinone (NMP), dimethylsulphoxide(DMSO), alcohols, ethyleneglycol ethers such as for examplemonoethyl-diethyleneglycol, propyleneglycol ethers, dioxane and toluene.

Finally, the activator can consist of one or more palladium complexesselected from the group consisting of:

complexes having the formula (I), wherein:

-   -   R1 is H, R2 is CH₂CH₂NH₂ and X is Cl, a complex named        (diethylenetriamine)(dichloro) palladate (II);    -   R1 and R2 are identical and are CH₂CH₂OH and X is Cl, a complex        named        (N,N′-bis(2-hydroxyethyl)ethylenediamine)-(dichloro)palladate        (II);

complexes having the formula (IIa) wherein:

-   -   R1 is H, R2 is CH₂CH₂NH₂ and Y is two Cl, a complex named        trans-bis(diethylenetriamine) palladate (II);

complexes having the formula (IIb) wherein:

-   -   R1 is H, R2 is CH₂CH₂NH₂ and Y is two Cl, a complex named        cis-bis(diethylenetriamine)palladate (II);        at a concentration comprised between 5×10⁻⁵ M and 5×10⁻⁴ M.

For more information, one can refer to the description of the patentapplication FR 2 950 634.

The method of preparing a bilayer coating (insulator/barrier layer) thathas just been described is especially useful in the preparation ofthrough-vias 50, especially of integrated circuits, for constituting theinternal structure, which can optionally be coated with a copper seedlayer 80 enabling the metallization of the through-vias.

The aforementioned copper seed layer 80 can also be produced by a wetdeposition method, preferably in a liquid medium.

For such purpose, WO 2010/001054 discloses a method (step 600) ofpreparing a coating of the semiconductor substrate, said coatingconsisting of an internal first layer forming the electricallyinsulating film 60, an intermediate second layer forming the copperdiffusion barrier 70, and a third, external copper seed layer 80, whichlayer is produced by bringing the free surface of the second layer intocontact with a liquid solution comprising:

at least one solvent;

copper ions in a concentration of between 14 and 120 mM;

ethylenediamine;

the molar ratio of ethylenediamine to copper being between 1.80 and2.03;

the pH of said composition being between 6.6 and 7.5;

b) polarization of said free surface of the second layer for asufficient duration to form said third layer.

As will be understood, this step makes it possible to carry outmetallization of the vias 50.

The liquid solutions employed in this step make it possible to obtain acopper seed layer 80 leading to a particularly high coverage rate(greater than 99%) of the substrate including in the most critical areasof the vias, and this even when the structure has a high form factor(aspect ratio greater than 3:1, or even of the order of 10 to 15:1) anda relatively high via volume (from 0.8×10¹ to 5×10⁶ μm³). These liquidsolutions are therefore perfectly compatible with a use at theindustrial scale.

One preferred family of liquid solutions employed in step C. comprisesthose whose copper ions are present in a concentration of between 16 and64 mM.

Another preferred family of liquid solutions comprises those whose molarratio of copper ions to ethylenediamine is between 1.96 and 2.00.

The through-via can then be metallized by filling with copper inaccordance with the usual methods.

Alternatively, metallization of the through-via is performed withoutcoating the barrier layer 70 with a seed layer 80, by direct filling ofthe via (coated with the insulating layer 60 and the barrier layer 60only) in accordance with the description of the French patentapplication no. FR 10 54668.

In that purpose, metallization of the via is obtained byelectrodepositing copper with a composition comprising:

copper ions, said copper ions having a concentration of 45 to 1500 mM,preferably 45 to 500 mM, and more preferably 100 to 300 mM;

a complexing agent for copper, comprising at least one component of thegroup comprising the aliphatic polyamines having 2 to 4 amino groups,said complexing agent for copper having a concentration of 45 to 3000mM, preferably 45 to 1500 mM, and more preferably 300 to 900 mM;

The complexing agent for copper can be, for example, ethylenediamine,diethylenediamine, triethylenediamine or dipropylenetriamine, preferablyethylenediamine.

the molar ratio between copper and said complexing agent for copperbeing of 0.1 to 5, preferably 0.1 to 1, and more preferably 0.2 to 0.4;

thiodiglycolic acid, said thiodiglycolic acid having a concentration of1 to 500 mg/L; and

optionally, a buffering system, in particular ammonium sulphate, in aconcentration of 0.1 to 3 M.

In accordance with an embodiment, the solvant is water, and the copperions come from copper (II) sulfate.

EXAMPLE

After the wet etching step, the resulting substrate (coupon of 4×4 cm insize) is washed in deionised water in an ultrasonic bath (320 W, 35KHz), treated with a modified piranha solution (60 ml H₂O₂+15 mL puresulphuric acid+1 ml of a 100 ppm HF solution) for 3 minutes also in anultrasonic bath (320 W, 35 KHz). The use of Teflon vessels or equivalentis required. The coupon is finally prewetted with deonised water andsubmitted to electrografting of P4VP.

The electrografting solution employed in this example is an aqueoussolution prepared by introducing 5 mL of 4-vinylpyridine (4-VP; 4.5×10⁻²mol) into 95 ml of HCl 1M, then adding to the mixture 236 mg ofcommercially available 4-nitrobenzenediazonium tetrafluoroborate (DNO₂;1×10⁻³ mol).

The methods that have just been described make it possible to fabricatewafers of conductor or semiconductor material, especially made ofsilicon, with a novel structure.

Protocol

To carry out electrografting on the silicon substrate a system has beenused which is composed of:

a sample holder equipped with means for rotating at a predeterminedspeed and shaped to support the substrate, the assembly thus constitutedbeing intended to serve as the working electrode;

a carbon sheet intended to serve as the counter-electrode;

a stabilized electrical power supply and electrical connection device.

The electrografting of the P4VP onto the surface of the siliconsubstrate has been carried out by applying to the substrate, previouslycaused to rotate at a speed of 40 to 100 rpm (60 rpm in the example), a“pulsed voltage” electrochemical protocol for a predetermined durationof around 10 to 30 minutes (15 minutes in the example).

a total period P of between 0.01 and 2 seconds (0.6 seconds in theexample);

a polarization time T on of between 0.01 and 1 s (0.36 seconds in theexample) during which a potential difference of 5 V to 20 V is appliedto the surface of the substrate (cathode potential of −17 V in theexample); and

an idle period with zero potential, called T off, of a duration ofbetween 0.01 and 1 s (0.24 seconds in the example).

The duration of this electrografting step depends, as will beunderstood, on the desired thickness of the polymer insulating layer 60.

Once the electrografting is finished, the sample is washed severaltimes, first with water, then with dimethylformamide (DMF), and finallyonce again with deionised water. The drying of the sample is carried outin an inert atmosphere typically at 250° C. during 10 minutes.

The carrier 35 is then withdrawn from the semiconductor structure 1.

The invention claimed is:
 1. A method for forming a vertical electricalconnection in a layered semiconductor structure, comprising thefollowing steps: providing a layered semiconductor structure, saidlayered semiconductor structure comprising: a support substrateincluding a first surface and a second surface, an insulating layeroverlying the first surface of the support substrate, and at least onedevice structure formed in the insulating layer; and drilling a via fromthe second surface of the support substrate up to the device structure,in order to expose the device structure, drilling of the insulatinglayer being at least partially performed by wet etching; wet coating thevia with an insulating film by bringing a surface of said via intocontact with a liquid solution, in order to obtain a uniform insulatingfilm, wherein the wet coating of the via is selective and only coats thevia in the vicinity of the support substrate and preparing a copperdiffusion barrier by forming by a wet process, at the surface of theinsulating film, an organic film containing particles of metals or metalalloys.
 2. The method of claim 1, wherein wet etching is performedduring a predetermined time, said predetermined time depending on thematerial of the insulating layer, the etchant and the thickness of theinsulating layer to be drilled.
 3. The method of claim 1 or 2, whereinwet etching is performed with a solution containing fluorhydric acid,and optionally glycerol.
 4. The method of claim 3, wherein the etchantcomprises between 0.5% and 50% in volume of Fluorhydric acid, preferably1.35%.
 5. The method of claim 3 or 4, wherein the etchant furthercomprises between 0.5 and 50% in volume of glycerol, preferably 1.35%.6. The method of anyone of claims 1 to 5 further comprising apre-wetting step prior to the wet etching step, wherein the layeredsemiconductor structure is plunged in water.
 7. The method of anyone ofclaims 1 to 6 further comprising a rinsing step following the wetetching step, wherein the layered semiconductor structure is rinsed withwater.
 8. The method of anyone of claims 1 to 7 further comprising avacuum step following the wet etching step, wherein the layeredsemiconductor structure is submitted to a controlled vacuum.
 9. Themethod of claim 8, wherein the layered semiconductor structure isplunged in water during the vacuum step.
 10. The method of anyone ofclaims 1 to 9 further comprising a removal step before the wet etchingstep, wherein the support substrate is thinned.
 11. The method of anyoneof claims 1 to 10 further comprising a pre-drilling step before the wetetching step, wherein a pre via is formed from the second surface up toat least the insulating layer.
 12. The method of claim 11, wherein thepre via is formed by dry etching, wet etching or reactive ion etching.13. The method of claim 1, wherein the solution comprises: a proticsolvent; at least one diazonium salt; at least one monomer that ischain-polymerizable and soluble in said protic solvent; at least oneacid in a sufficient quantity to stabilize said diazonium salt byadjusting the pH of said solution to a value less than 7, preferablyless than 2.5; and wherein the surface of said vertical connection ispolarizes according to a potentio- or galvano-pulsed mode for a durationsufficient to form a film having a thickness of at least 60 nanometers,and preferably between 80 and 500 nanometers.
 14. The method of claim 1,wherein the particles of metal or metal alloys of the organic film maycomprise nanoparticles wherein the metal or metal alloy may comprise andthe step of preparation of the copper diffusion barrier furthercomprises, nickel or cobalt; bringing the film thus formed into contactwith a liquid solution containing at least one metal salt, preferably ofthe same nature as the metal incorporated into the organic film, astabilizing agent, and at least one reducing agent under conditionsenabling the formation of a metal film having a thickness of at least100 nm.
 15. The method of claim 1, further comprising the preparation ofa copper diffusion barrier by:
 1. activating the surface of theinsulating layer with a solution comprising: i) an activator constitutedof one or several palladium complexes chosen in the group consisting of:palladium complexes having the formula:

wherein: R1 and R2 are identical and represent H; CH₂CH₂NH₂; CH₂CH₂OH;or R1 represents H and R2 represents CH₂CH₂NH₂; or R2 representsCH2CH2NHCH2CH2NH2 and R1 represents CH₂CH₂NH₂; or R2 representsCH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂ and R₁ represents H; X represents a ligandchosen in the group consisting of Cl⁻; Br⁻; I⁻; H₂O, NO₃ ⁻; CH₃SO₃ ⁻;CF₃SO₃ ⁻; CH₃-Ph-SO₃ ⁻; CH₃COO⁻; palladium complexes having the formulaor:

wherein: R1 and R2 are defined as above-mentioned, and Y represents acounter-ion comprising two negative charges constituted: either of twomono-anions preferably chosen in the group consisting of Cl⁻; PF₆ ⁻; BF₄⁻; NO₃ ⁻; CH₃SO₃ ⁻; CF₃SO₃ ⁻; CH₃C₆H₄SO₃; CH₃COO⁻; or of a di-anion,preferably SO₄ ²⁻; ii) an bi-functional organic binder constituted ofone or several organosilanes having the general formula:{NH₂-(L)}_(3-n)-Si(OR)_(n) wherein: L is a spacer selected from thegroup consisting of CH₂; CH₂CH₂; CH₂CH₂CH₂— and CH₂CH₂NHCH₂CH₂; R is agroup selected from the group consisting of CH₃, CH₃CH₂, CH₃CH₂CH₂, ₂CH;and n is an integer equal to 1, 2 or 3, iii) a solvent systemconstituted of one or several solvents suitable for solubilising saidactivator and said binder;
 2. electrolessly depositing a metallic layeron the activated surface.
 16. The method of claim 14 or 15, furthercomprising the preparation of a copper seed layer by: a) bringing thefree surface of the copper diffusion barrier layer into contact with aliquid solution comprising: at least one solvent; copper ions in aconcentration of between approximately 14 and 120 mM; ethylenediamine;the molar ratio of ethylenediamine to copper being between 1.80 and2.03; the pH of said composition being between 6.6 and 7.5; b)polarizing said free surface of the second layer for a sufficientduration to form said copper seed layer.
 17. The method of claim 16,further comprising a step of metallization of the vertical electricalconnection by electrodepositing copper with a composition comprising:copper ions, said copper ions having a concentration of 45 to 1500 mM,preferably 45 to 500 mM, and more preferably 100 to 300 mM; a complexingagent for copper, comprising at least one component of the groupcomprising the aliphatic polyamines having 2 to 4 amino groups, saidcomplexing agent for copper having a concentration of 45 to 3000 mM,preferably 45 to 1500 mM, and more preferably 300 to 900 mM; the molarratio between copper and said complexing agent for copper being of 0.1to 5, preferably 0.1 to 1, and more preferably 0.2 to 0.4;thiodiglycolic acid, said thiodiglycolic acid having a concentration of1 to 500 mg/L; and optionally, a buffering system, in particularammonium sulphate, in a concentration of 0.1 to 3 M.
 18. A method forforming a vertical electrical connection in a layered semiconductorstructure, comprising the following steps: providing a layeredsemiconductor structure, said layered semiconductor structurecomprising: a support substrate including a first surface and a secondsurface, an insulating layer overlying the first surface of the supportsubstrate, and at least one device structure formed in the insulatinglayer; and drilling a via from the second surface of the supportsubstrate up to the device structure, in order to expose the devicestructure, drilling of the insulating layer being at least partiallyperformed by wet etching; wet coating the via with an insulating film bybringing a surface of said via into contact with a liquid solution, inorder to obtain a uniform insulating film, wherein the wet coating ofthe via is selective and only coats the via in the vicinity of thesupport substrate, wherein the solution comprises: a protic solvent; atleast one diazonium salt; at least one monomer that ischain-polymerizable and soluble in said protic solvent; and at least oneacid in a sufficient quantity to stabilize said diazonium salt byadjusting the pH of said solution to a value less than 7, preferablyless than 2.5.
 19. The method of claim 18, wherein the surface of saidvertical connection is polarized according to a potentio- orgalvano-pulsed mode for a duration sufficient to form a film having athickness of at least 60 nanometers, and preferably between 80 and 500nanometers.
 20. A method for forming a vertical electrical connection ina layered semiconductor structure, comprising the following steps:providing a layered semiconductor structure, said layered semiconductorstructure comprising: a support substrate including a first surface anda second surface an insulating layer overlying the first surface of thesupport substrate, and at least one device structure formed in theinsulating layer; and drilling a via from the second surface of thesupport substrate up to the device structure, in order to expose thedevice structure, drilling of the insulating layer being at leastpartially performed by wet etching; wet coating the via with aninsulating film by bringing a surface of said via into contact with aliquid solution, in order to obtain a uniform insulating film, whereinthe wet coating of the via is selective and only coats the via in thevicinity of the support substrate, and preparing a copper diffusionbarrier by activating the surface of the insulating layer with asolution comprising: i) an activator constituted of one or severalpalladium complexes, ii) an bi-functional organic binder, iii) a solventsystem constituted of one or several solvents suitable for solubilizingsaid activator and said binder.
 21. The method of claim 20, wherein: i)the one or several palladium complexes are chosen in the groupconsisting of: palladium complexes having the formula: R1 N N R2 Pd X X(I) wherein: R1 and R2 are identical and represent H; CH2CH2NH2;CH2CH2OH; or R1 represents H and R2 represents CH2CH2NH2; or R2represents CH2CH2NHCH2CH2NH2 and R1 represents CH2CH2NH2; or R2represents CH2CH2NHCH2CH2NHCH2CH2NH2 and R1 represents H; X represents aligand chosen in the group consisting of Cl—; Br—; I—; H2O, NO3-;CH3SO3-; CF3SO3-; CH3-Ph-SO3-; CH3COO—; palladium complexes having theformula or: Y2- Y2- R1 N N R2 R1 N N R2 Pd R2 N N R1 R1 N N R2 Pd (IIa)(IIb) 2+ wherein: R1 and R2 are defined as above-mentioned, and Yrepresents a counter-ion comprising two negative charges constituted:either of two mono-anions preferably chosen in the group consisting ofCl—; PF6-; BF4-; NO3-; CH3SO3-; CF3SO3-; CH3C6H4SO3-; CH3COO—; or of adi-anion, preferably SO4²⁻; ii) the bi-functional organic binder isconstituted of one or several organosilanes having the general formula:{NH2-(L)}3-n-Si(OR)n wherein: L is a spacer selected from the groupconsisting of CH2; CH2CH2; CH2CH2CH2- and CH2CH2NHCH2CH2; R is a groupselected from the group consisting of CH3, CH3CH2, CH3CH2CH2, 2CH; and nis an integer equal to 1, 2 or 3, and the step of preparation of thecopper diffusion barrier further comprises electrolessly depositing ametallic layer on the activated surface.